Catalytic process for preparing unsaturated acids and aldehydes



United States Patent 3,520,923 CATALYTIC PROCESS FOR PREPARING UNSATU- RATED ACIDS AND ALDEHYDES Jamal S. Eden, Akron, Ohio, assignor to The B. F. Goodrich Company, New York, N.Y., a corporation of New York No Drawing. Filed Feb. 28, 1967, Ser. No. 619,190 Int. Cl. C07c 51/32 US. Cl. 260-533 '7 Claims ABSTRACT OF THE DISCLOSURE Unsaturated aldehydes and unsaturated acids as acrolein and acrylic acid, and methacrolein and methacrylic acid, are simultaneously prepared by reacting an unsaturated monoolefinic hydrocarbon as propylene or isobutylene with oxygen in the presence of a catalyst containing molybdenum, tellurium, oxygen, thorium and phosphorous, at elevated temperatures.

BACKGROUND OF THE INVENTION they are not sufficiently selective, so that the hydrocarbon molecule is attacked at both the olefinic unsaturation and at a methyl group; or the oxidation of the olefin either does not proceed beyond the aldehyde stage or goes all the way to the acid.

SUMMARY OF THE INVENTION This invention relates to catalysts comprising a mixture of a molybdenum, tellurium, oxygen, thorium and phosphorous in a molar ratio, calculated as, 100 M00 10-100 TeO and 10-100 of a thorium phosphate, and to a method of preparing acrolein and acrylic acid, or methacrolein and methacrylic acid by passing vapors of propylene or isobutylene and an oxygen containing gas over the catalyst at a temperature of from about 300 C. to about 550 C. The catalyst can also be designated as M01oTe1 Th 2 P2 20O39 12o the P being in the form of a phosphate, i.e., each P is attached to 3 or 4 oxygen atoms and the ratio of Th to P is from 1:2 to 3:4.

The catalysts of this invention have long life and will convert a substantial amount, more than 50% per pass, of a gaseous monoolefin such as propylene or isobutylene to yield high proportions of both acrolein and acrylic acid, or methacrolein and methacrylic acid. The catalyst also produces a wide ratio of olefinic aldehyde to monoolefinically unsaturated carboxylic acid by controlling reaction conditions or catalyst composition. Mol percent efliciencies as high as about 40 for the aldehyde and about 50 ice for the unsaturated carboxylic acid have been obtained with the catalyst and process of this invention. Usually when the efiiciency for conversion of the hydrocarbon to aldehyde is high the efiiciency for the conversion to acid is lower and vice versa. This provides a degree of flexibility in the process, so as to provide means for obtaining a product mix that is needed at any particular time during commercial operation.

DETAILED DESCRIPTION The reactants The essential reactants are (1) propylene or isobutylene and (2) an oxygen-containing gas, which can be pure oxygen, oxygen diluted with an inert gas, oxygen enriched air or air without additional oxygen. For reasons of economy, air is the preferred oxygen-containing reactant.

For the purpose of this invention the hydrocarbons which are oxidized can be defined generically by the formula H (CH2)o-1 CH3- 0:0 H5

The end products formed result from the oxidation of only one methyl group on the hydrocarbon molecule while the terminal CH =C remains intact.

Stoichiometric ratios of oxygen to olefin for the purpose of this invention are 1.5 to 4 to 1. Slightly lower amounts of oxygen can be used at a sacrifice of yield. It is preferred to use 33 to 66% excess oxygen. Larger excesses do not impair the yields of aldehydes and acids, but for practical considerations an excess much above would require extremely large equipment for a given production capacity, particularly if air is used.

The addition of steam into the reactor along with the hydrocarbon and oxygen-containing gas is desirable but not absolutely essential. The function of steam is not clear, but it seems to reduce the amount of carbon monoxide and dioxide in the efiiuent gases. Other diluent gases can be used. Saturated hydrocarbons such as propane are rather inert under the reaction conditions. Nitrogen, argon, krypton or other known inert gases can be used as diluents if desired but are not preferred because of the added cost.

The catalyst and its preparation There are several methods for the preparation of the catalyst, which can be supported or unsupported. It is possible to dissolve each of the starting ingredients in water and combine them from the aqueous solutions or the ingredients can be dry blended. Because of the more uniform blend obtained by the solution procedure, it is preferred.

A general procedure for preparing a catalyst from water soluble ingredients is to (1) dissolve the requisite amount of a molybdenum salt, a tellurium salt and a thorium salt in water (2) add the requisite amount of phosphoric acid to the thorium salt solution, ,(3) add the tellurium salt solution to the molybdenum salt solution,

and (4) then add the thorium salt-phosphoric acid mixture to the moly-bdenum-tellurium salt mixture. The catalyst is then dried and baked at 400 C. for about 16 hours.

Supported catalysts can be prepared by adding a dry support or an aqueous slurry thereof to the aqueous solution of catalyst or the aqueous catalyst ingredients can be added to the slurry of the support. Alternatively a slurry of the catalyst ingredients can be prepared in water, then dried and baked. For supported catalysts the aqueous slurry of the catalyst ingredients can be added to an aqueous suspension of the support or vice versa, and then dried and baked. Another method is to blend the dry ingredients of the desired particle size and then mix them thoroughly. Thorough blending and uniform particle size is desired.

A specific example (A) of the solution method is as follows: 7

(1) Dissolve 158.94 g. of (NH Mo O -4H in 450 ml. of water.

(2) Dissolve 47.88 g. of TeO in 100 ml. conc. HCl and add to (1).

(3) Dissolve 165.67 g. of Th(NO -4H O in water and add 69.2 g. of 85% H PO Add this mixture slowly to the mixture of (1) and (2).

Dry on a steam bath and calcine in a hot tube oven for 16 hours at 400 C. Thereafter, the catalyst is ground to the desired mesh size and sieved.

An example (B) of preparations of a supported catalyst 1s:

1) Dissolve 79.47 g. of (NH Mo-;O -4H O in 300 ml. of water and add to 90 grams of catalyst silica in 200 ml. of Water. (Microspheroidal silica Ludox HS.)

(2) Dissolve 23.94 g. of Te0 in 50 ml. of concentrate HCl and mix with (1).

(3) Dissolve 82.83 g. of Th(NO '4H O in 200 ml. of water and add 34.6 g. of 85% H PO This mixture was added slowly to the mixture of (1) and (2).

Dry on a steam bath and bake in a hot tube for 16 hours at 400 C. Thereafter, the catalyst is ground to the desired mesh size for fixed or fluid bed reactions and sieved.

Among the suitable supports are silica, silica containing materials, such as diatomaceous earth, kieselguhr, silicon carbide, clay, aluminum oxides and even carbon, although the latter tends to be consumed during the reaction.

Such catalysts, with molar ratios of 100 Mo, -100 Te and 10-100 of a thorium phosphate can be used for oxidizing the monoolefinic hydrocarbon to aldehyde and/ or carboxylic acid. The catalyst contains chemically bound oxygen so that the generic formula can be written as M00 TeO ThP O or other thorium phosphate 10100. The phosphate can be a PO; radical, a pyrophosphate, or a polyphosphate.

Reaction conditions The reaction can be carried out in either a fixed or fluidized catalyst bed.

The reaction temperature can range from about 300 C. to 550 C. For the oxidation of propylene, the preferred range is from about 350 C. to about 450 C. Below 350 C. the conversion per pass is lower and low temperature tends to produce more aldehyde. Usually, a longer contact time is needed at lower temperatures to obtain the yields of desired products obtainable at higher temperatures. Above 450 C. in the propylene oxidation, some of the desired end products appear to be oxidized to carbon oxides. For isobutylene, oxidation temperatures of 37S550 C. are desirable with the preferred range being 380-475 C.

The molar ratio ofoxygen to propylene or isobutylene should be at least 2 to 1 for good conversion and yields. Sorne excess oxygen, 33 to 66 mol percent is even more desirable and is preferred. There is no critical upper limit as to the amount of oxygen, but when air is used as the oxygen-containing gas it becomes apparent that too great an excess will require large reactors, pumps, compressors and other auxiliary equipment for any given amount of desired end product. It is therefore best to limit the amount of air to provide a 33 to 66% excess of oxygen. This range provides the largest proportion of acid, under given reaction conditions. Also, since care is needed to avoid an explosive mixture, the limiting of air aids in that direction.

The mol ratio of steam to propylene or isobutylene can range from 0 to about 5 to 7, but best results are obtained with molar ratios of about 3 to 5 per mol of olefin and for this reason are preferred.

The contact time can vary considerably in the range of about 2 to 70 seconds calculated at 25 C. and 760 mm. Best results are obtained in a range of about 8 to 54 seconds and this range is preferred. Longer contact times usually favor the production of acid at any given temperature.

The particle size of catalyst for fixed bed operations used is from 10-18 mesh, passes 10 mesh, held on 18 (U.S.). As is known, for fixed beds, the size may be of a wide range of particle sizes. For fluid bed systems, a useful catalyst size is to pass and be held on 325 mesh (U.S.).

The reaction can be run at atmospheric pressure, in a partial vacuum or under induced pressure up to 50-100 p.s.i. Atmospheric pressure is preferred for fixed bed systems and a pressure of 1 to p.s.i. for fluid bed reactions. Operation at a pressure which is below the dew point of the unsaturated acid at the reaction temperature is advantageous The data in the examples show that wide variations in percentages of unsaturated acids and aldehydes can be obtained with a single catalyst, using fixed ratio of reactants but changing the temperature and/or contact time. Further variation is obtainable by controlling the other variables in the reaction including the catalyst compositions within the limits set forth herein.

EXAMPLES 1-5 A series of runs were made in a fixed bed reactor of a high silica (Vycor) glass tube 12 inches long and 30 mm. outer diameter. The reactor had three inlets, one for air, one for steam and one for propylene. Three external electrically operated heating coils were wound on the reactor. One of the coils extended along the entire length of the reactor and each of the remaining coils extended only about one-half the length of the reactor. Outlet vapors were passed through a short water cooled condenser. Uncondensed gases were passed through a gas chromatograph (Perkin-Elmer model 154D) and analyzed continuously. The liquid condensate was weighed and then analyzed for acrylic acid and acrolein in the gas chromatograph. The reactor was filled with ml. of unsupported catalyst made by the solution method (A) described above, using a ratio of 75 M00 25 TeO and 25 ThP O Empirically the catalyst is and the P is present as P O-r The catalyst was not supported and had a mesh size of 10-18 (U.S. Sieve). Steam at a temperature of 200-250 C. was first passed into the reactor. Then propylene and air were separately fed into the stream of water vapor. This mixture then passed through a preheater and entered the reactor at about 200250 C. The reactor was preheated to about 285 C. before the gas feed was begun. The ratio of reactants per mol of propylene, contact time (STP), the reaction temperature in C., and the data obtained in these runs is summarized in the Table A below.

consisting essentially of molybdenum, tellurium, thorium, oxygen and phosphorous, present on a molar basis, cal- TABLE A Mol percent yield on Mol propylene M01 percent Contact percent converted efficiency Run Oxygen, Steam, Temp., Time, propylene No. mols mols 0. seconds converted Aer AA Aer. AA

Acr.=Acrolein; AA=Acrylic Acid.

EXAMPLES 69 culated as, molybdenum oxide 100, tellurium oxide 10- A supported catalyst prepared according to procedure (B) above was prepared to the ratio 75 Mo0 -25 TeO -25 ThP -O ZSO SiO The particle size was between 80 and 325 mesh (UgS. Sieve). The runs were made in a fluidized bed. In these runs the reactor was a high silica glass cylinder with an CD. of 38 mm. and height of 12 inches. It was filled to a height about 4 inches (85 ml.). In all cases'the catalyst was fluidized by first injecting hot air into the reactor and then adding the requisite amounts of steam and propylene. The gases were preheated to about 250 C. prior to entering the reactor. The reactorwas heated externally with electrical resistance wire, and the reaction temperature was controlled by use of rheostats. The reaction conditions, ratio of 100 and a thorium phosphate 10-100.

2. The method of claim 1 wherein the aldehyde is acrolein, the acid "is acrylic acid, the hydrocarbon is propylene, the amount of oxygen is from about 2 to 4 mols, the temperature is about 300 C. to about 450 C. and the catalyst consists essentially of a molar ratio of 100 M00 10100 TeO' and 10-100 thorium pyrophosphate.

3. The method of claim 1 wherein the aldehyde is methacrolein, the acid is methacrylic, the hydrocarbon is isobutylene, the catalyst is 100 M00 10-100 TeO and 10-100 thorium pyrophosphate and the temperature is from about 380 C. to about 475 C.

4. The method of claim 2 wherein the mols of oxygen are from 2 to 3 and the mols of steam are about 2 to 6.

5. The method of claim 3 wherein the mols of oxygen reactants and results are set forth in Table B. are about 2 to 3 and the mols of steam are about 2 to 6.

TABLE B Moi percent yield on Oxygen, Steam. Mol propylene M01 percent mols/ mols/ Contact percent converted efficiency Run moi n1 time, Temp., propylene No. 03H; C3119 seconds C. converted Aer. AA Are. AA

Acr.=Acro1eln; AA=Acrylio Acid. A

I claim: '1 6. The method of claim 1 wherein the reaction is 1. A method of preparing a mixture of unsubstituted conducted with a fixed bed catalyst. monoolefinic aldehydes and monoolefinic monocarboxylic 45 7. The method of claim 1 wherein the reaction is acids by oxidation of a methyl group of a monoolefinic conducted with a fluid bed catalyst. hydrocarbon having the structure References Cited (C5904 UNITED STATES PATENTS CHFC=CH2 3,401,196 9/1968 Eden 260 533 3,445,500 5/1959 Eden 260-533 comprising passing over a catalyst gases having a molar ratio of 1 mol of said monoolefinic hydrocarbon, an LORRAINE A'WEINBERGER Pnmary Exammer oxygen-containing gas containing about 1.5 to 4 mols D. E. STENZEL, Assistant Examiner of oxygen and 0 to 7 mols of water vapor, per mol of said monoolefinic hydrocarbon, at a temperature of from about 300 C. to about 550 C., said catalyst US. Cl. X.R. 

